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研究生:廖健良
研究生(外文):Liao, Jianliang
論文名稱:以層狀磷酸鈦固體酸做為酚溴化反應觸媒之研究
論文名稱(外文):Bromination of Phenol by Using a Layered Titanium Phosphate HTP as a Catalyst
指導教授:李英正李英正引用關係
指導教授(外文):Li, Yingjeng
口試委員:陳順基鄭光煒
口試委員(外文):Chen, ShunchiCheng, Kongwei
口試日期:2012-01-04
學位類別:碩士
校院名稱:明志科技大學
系所名稱:化學工程研究所
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2012
畢業學年度:100
語文別:中文
論文頁數:91
中文關鍵詞:層狀磷酸鈦溴化反應固體酸催化
外文關鍵詞:layered titanium phosphatephenolbrominationsolid acidcatalysis
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本研究使用不同的觸媒進行酚之溴化反應,藉以瞭解這些觸媒的功能。酚的溴化反應中使用 KBr 做為溴源、H2O2 做為氧化劑、醋酸做為溶劑,反應時間分別為 0.5、1、2、4 小時,反應溫度分別為室溫、低溫(15℃)。
對酚的溴化反應主要分為三組:(1)使用層狀磷酸鈦(HTP)固體酸,(2)使用酸性陽離子交換樹脂(Amberlyst-15),(3)無添加觸媒。利用氣相層析儀(GC)對三組反應產物做定量分析,可得知三組之間的反應結果差異,並進行探討。
無觸媒的反應結果顯示反應產物以4-溴酚為主,對照使用陽離子樹脂或層狀磷酸鈦的反應結果,可觀察到對4-溴酚產物的選擇性較好,對2-溴酚產物的選擇性較差。
使用層狀磷酸鈦為觸媒在酚的溴化反應中,反應時間2小時、反應溫度為室溫的條件下可得到3組反應中最高的轉化率92%。推測可能是層狀磷酸鈦的表面積較陽離子交換樹脂大,因此可與更多的反應物接觸進行催化反應,或是由於層狀磷酸鈦表面分佈較多的布忍斯特酸進行催化而獲得較高轉化率。
本研究亦對層狀磷酸鈦(HTP)固體酸進行表面積與孔徑分析,其平均表面積為9.15 m2/g,平均吸附孔徑為1.57μm。

Bromination of phenol was studied by using different kinds of catalysts. Potassium bromide was employed as the source of bromine, hydrogen peroxide as oxidant, acetic acid as solvent. The reactions were carried out at different temperatures and various reaction times.
The reactions were also categorized into three groups: (1) using layered titanium phosphate (HTP) solid acid as catalyst, (2) using proton type cationic exchange resin Amberlyst-15 as catalyst, (3) using no catalyst. Gas chromatography was employed for the analysis of the reaction results.
It was found that the reaction using HTP as catalyst with reaction time of 2 hours at room temperature gave the highest yield of 92%. It is possibly due to the larger surface area, which is 9.15 m2/g obtained from BET experiment, of the HTP powder with comparison to that of Amberlyst-15.

明志科技大學碩士學位論文指導教授推薦書 I
明志科技大學碩士學位論文口試委員審定書 II
明志科技大學學位論文授權書 III
誌謝 IV
明志科技大學 IV
摘要 V
Abstract VI
圖目錄 IX
表目錄 XI
表目錄 XI
第一章 緒論 1
1.1 前言 1
1.2 研究動機 2
第二章 相關理論與文獻回顧 4
2.1 相關原理 4
2.1.1水熱合成法 4
2.1.2 X光繞射分析儀 5
2.1.3 親電性芳香取代反應原理 7
2.1.4取代基的配位效應 10
2.1.5氣相層析儀(Gas chromatography) 10
2.2 文獻回顧 11
2.2.1 酚的特性 11
2.2.2 酚主要產物的應用 12
2.2.3 酚的反應 14
2.2.4 酚的溴化反應 17
2.2.5 觸媒的特性 23
2.2.6固體酸觸媒 24
2.2.7陽離子交換樹脂 26
2.2.8磷酸鈦觸媒 27
第三章 實驗內容 29
3.1 實驗藥品與器材 29
3.1.1 實驗藥品 29
3.1.2 實驗器材 31
3.2 實驗步驟 32
3.2.1 合成層狀磷酸鈦(HTP)觸媒 33
3.2.2以XRD鑑定觸媒 33
3.2.3 酚的溴化反應 34
3.2.4 製做檢量線 36
3.2.5 產物的GC定量分析配製 40
第四章 結果與討論 41
4.1層狀磷酸鈦(HTP)觸媒做XRD的鑑定 41
4.2層狀磷酸鈦(HTP)觸媒FE-SEM掃描分析 43
4.3層狀磷酸鈦(HTP)的表面積與孔徑分析結果 45
4.4將產物做GC-MS定性分析 46
4.5 標準品檢量線與層析圖 50
4.6 將產物做GC定量分析 59
4.7酚的溴化反應討論 69
4.7.1酚的溴化反應 69
4.7.2各組反應在溴化反應中的轉化率結果比較 70
4.7.3改變反應溫度對各組反應轉化率的影響 73
4.7.4反應產物選擇率以及反應產物受熱力、動力控制的比較 76
第五章 結論 83


【1】P. V. Vyas, A. K. Bhatt, G. Ramachandraiah, A. V. Bedekar, “Environmentally benign chlorination and bromination of aromatic amines, hydrocarbons and naphthols”Tetrahedron Letters 44,P4085(2003).
【2】M. Kuroboshi, Y. Waki, H. Tanaka, “Palladium-Catalyzed Tetrakis(dimethylamino)ethylene-Promoted Reductive Coupling of Aryl Halides”J. Org. Chem.68,P3938(2003).
【3】J.M. Chre´tien, F. Zammattio, E. Le Grognec, M. Paris, B. Cahingt, G. Montavon, J.P. Quintard, “Polymer-Supported Organotin Reagents for Regioselective Halogenation of Aromatic Amines”J. Org. Chem.70, P2870(2005).
【4】A. Molinari, G. Varani, E. Polo, S. Vaccari, A. Maldotti, “Photocatalytic and catalytic activity of heterogenized W10O324− in the bromide-assisted bromination ofarenes and alkenes in the presence of oxygen”Journal of Molecular Catalysis A: Chemical 262,P156(2007).
【5】A. Butler, J.V. Walker,“Marine haloperoxidases”Chem. Rev.93, P1937(1993).
【6】B.G. McKinnie, “Process for the preparation of tetrabromobisphenol-A”Bonnie, to Albemarle Corporation. US Patent 6,002,050 ,P1(1999).
【7】G.W. Gribble, “Naturally Occurring Organohalogen Compounds”Acc. Chem. Res:31,P141(1998)
【8】G.W. Gribble, “The diversity of naturally occurring organobromine compounds”Chem. Soc. Rev.28,P335(1999).
【9】J.M. Thomas, W.J. Thomas, “Principles and practice of heterogeneous catalysis”Wiley-VCH, Weinheim,P1(1997)
【10】K. Smith, “Highly Regioselective, Lewis Acid-FreeElectrophilic Aromatic Substitution”J. Chem. T.ech. Biotechnol.68,P432(1997).
【11】G.W. Morey, “hydrothermal synthesis”,Journal of the American ceramic society,36,P279(1983).
【12】黃啟倫“以水熱法合成 Mn-α-alumina/mullite/silica 粉體殼核結構”國立成功大學資源工程研究所碩士論文,P8(2006)。
【13】鄧建龍、姚潔宜、張茂男,“X光繞射分析在半導體工業上的應用”nano奈米通訊,第十五卷.第四期,P6(2008)。
【14】G.A. Olah, “Mechanism of Electrophilic Aromatic Substitutions”Acc. Chem.Res.4,P240(1970).
【15】王文德“電極及反應媒子對氯酚電解氧化影響之探討” 輔英科技大學環境工程衛生研究所碩士論文,P3(2004)。
【16】柯以侃“儀器分析”,新文京開發出版股份有限公司,P24(2005)。
【17】林經倫、陳昭雄、楊靜儀“有機化學” ,新文京開發出版股份有限公司,288,P310(2008)。
【18】江政傑“台灣西南海域沉積物中持久性有機化合物含量分佈之研究”國立中山大學海洋環境及工程研究所碩士論文,P3(2006)
【19】A. Smeds, P. Saukko, “Brominated flame retardants and phenolic endocrine disrupters in Finnish human adipose tissue”Chemosphere, 53,P1123(2003)
【20】N.R. Trivedi, S.B. Chandalia, “A Process Scheme Involving Transalkylation reactions to prepare o-Bromophenol from phenol” Organic Process Research & Development,3,P5(1999)
【21】C.F. Nutaitis, “The first total synthesis of the natural product angoluvarin”Tetrahedron Letters,51,P5497(2010)
【22】J. S. Dewar, “The mechanism of benzidine-type rearrangements, and the role of π-electrons in organic chemistry” J. Chem. Soc. 406,P777 (1946)
【23】H. Baines, “The mechanism of the bromination of phenol in aqueous solution”Journal of the Chemical Society, Trans.121,P2810(1922).
【24】W.S. Rapson, D.H. Saunder, E. Theal Stewart“Application of the conditions of the Tiemann–Reimer reaction to benzaldehyde”J.Chem. Soc.29,P74(1944).
【25】H. Wynberg, “The Reimer-Tiemann Reaction”Chem.Rev.60,P169(1960).
【26】A.S. Lindsey, H. Jeskey, “The Kolbe-Schmitt Reaction”Chem. Rev .57,P588(1957).
【27】S. Mallik, K.M. Parida, S.S. Dash, “Studies on heteropoly acid supported zirconia III:Oxidative bromination of phenol using phosphotungstic acid supported on zirconia”Journal of Molecular Catalysis A:Chemical 261,P172(2007).
【28】F.L. Lambert, W.D. Ellis, R.J. Parry, “Halogenation of Aromatic Compounds by N-Bromo- and N-Chlorosuccinimide under Ionic Conditions”J.Org.Chem. 30,P304(1965).
【29】N.B. Barhate, A.S. Gajare, R.D. Wakharkar, A.V. Bedekar, “Simple and Efficient Chlorination and Bromination of Aromatic Compounds With Aqueous TBHP(or H202) and a Hydrohalic Acid” Tetrahedron Letters.39,P6349 (1998)
【30】N. Narender, K.V.V. Krishna Mohan, R.V.Reddy, P. Srinivasu, S.J. Kulkarni, K.V. Raghavan, “Liquid phase bromination of phenols using potassium bromide and hydrogen peroxide over zeolites”J.Mol. Catal. A:Chem., 192,P73(2003).
【31】D.P. Das, K.M. Parida, “Liquid phase bromination of phenol over titania pillared zirconium phosphate and titanium phosphate”Catal. Commun. 7,P68(2006)
【32】H.A. Muathen,“1,8-Diazabicyclo[5.4.0]undec-7-ene hydrobromide perbromide: A new mild stable brominating agent for aromatic compounds”J. Org. Chem. 57,P2740(1992).
【33】L.F. Fieser, M. Fieser, “Reagents for Organic Synthesis” Wiley, New York, P967(1967).
【34】S. Kajigaeshi, T. Kakinami, H. Tokiyama, T. Hirakawa, T. Okamoto, “Bromination of phenols by use of benzyltrimethylammonium tribromide”Chem. Lett. P627(1987).
【35】V. Paul, A. Sudalai, T. Daniel, K.V. Srinivasan, “Regioselective bromination of activated aromatic substrates with N-bromosuccinimide over HZSM-5”Tetrahedron Letters.35,P7055(1994).
【36】K. Smith, G.A. El-Hiti, M.E.W. Hammond, D. Bahzad, Z. Li, C. Siquet, “Highly efficient and selective electrophilic and free radical catalytic bromination reactions of simple aromatic compounds in the presence of reusable zeolites”J. Chem. Soc., Perkin Trans.1,P2745(2000).
【37】K. Smith, D. Bahzad, “Highly efficient para-selective bromination of simple aromatic substrates by means of bromine and a reusable zeolite”Chem. Commun. P467(1996).
【38】F. Vega, Y. Sasson, K. Hhuddersman“Highly selective bromination of toluene in a bromine-oxirane-zeolite system” Zeolite.13,P341 (1993).
【39】J.H. Clark, J.C. Ross, D.J. Macquarrie, S.J. Barlow, T.W. Bastock“Environmentally friendly catalysis using supported reagents: the fast andselective bromination of aromatic substrates using supported zinc bromide”Chem. Commun. P1203 (1997).
【40】Z.X. Chen, G.C. Yang, “Bromination of phenols by bromine-supported resin”Yang, Hecheng Huaxue. 7,P435(1999).
【41】S.C. Roy, C. Guin, K.K. Rana, G. Maiti, “An efficient chemo and regioselective oxidative nuclearbromination of activated aromatic compounds using lithiumbromide and ceric ammonium nitrate”Tetrahedron Lett.42,P6941(2001).
【42】J.R. Hanson, S. Harpel, I.C. Rodriguez Medina, D. Rose, “Oxidative Bromination of Aromatic Amides using SodiumPerborate as Oxidant” J. Chem. Res. (S) P432(1997).
【43】M.H. Clague, A.J. Butler, “On the Mechanism of cis-Dioxovanadium(V)-CatalyzedOxidation of Bromide by Hydrogen Peroxide: Evidence for aReactive, Binuclear Vanadium(V) Peroxo Complex”J. Am. Chem. Soc .117,P3475(1995).
【44】D. Roche, K. Prasad, O. Repic, T.J. Blacklock, “Mild and regioselective oxidative bromination of anilines using potassium bromide and sodium perborate”Tetrahedron Letters .41,P2083(2000).
【45】U. Bora, G. Bose, M.K. Chaudhuri, S.S. Dhar, R. Gopinath, A.T. Khan, B.K. Patel, “Regioselective Bromination of Organic Substrates by Tetrabutylammonium Bromide Promoted by V2O5−H2O2: An Environmentally Favorable Synthetic Protocol”Org. Lett. 2,P247(2000).
【46】J.A.R.P. Sarma, A. Nagaraju, “Solid state nuclear bromination with N-bromosuccinimide. Part 1.Experimental and theoretical studies on some substituted aniline,phenol and nitro aromatic compounds”J. Chem. Soc., Perkin Trans.2,P1113(2000).
【47】Y. Goldberg, H. Alper, “Electrophilic halogenation of aromatics and heteroaromatics with N-halosuccinimides in a solid/liquid system using an H+ ion exchanger or ultrasonic irradiation”J. Mol. Cat. 88,P377(1994).
【48】B. Andersh, D.L. Murphy, R.J. Olson, “Hydrochloric Acid Catalysis of N-Bromosuccinimide(NBS) Mediated Nuclear Aromatic Brominations in Acetone” Synth. Commun.30,P2091 (2000).
【49】H. Konishi, K. Aritomi, T. Okano, J. Kiji, “A Mild Selective Monobromination Reagent System for Alkoxybenzenes; iV-Bromosuccinimide-Silica Gel” Bull. Chem. Soc. Jpn.62, P591(1989).
【50】T.J. Oberhauser, “A New Bromination Method for Phenols and Anisoles: NBS/HBF4•Et2O in CH3CN”J. Org. Chem.62,P4504(1997).
【51】B. Das, K. Venkateswarlu, A. Majhi, V. Siddaiah, K.R. Reddy, “A facile nuclear bromination of phenols and anilines using NBS in the presence of ammonium acetate as a catalyst” J. Mol. Catal. A: Chem. 267,P30(2007).
【52】M. Avramoff, J. Weiss, O. Schachter, “The Brominating Properties of Tetramethylammonium Tribromide1a” J. Org. Chem. 28,P3256(1963).
【53】D.P. Das, K.M. Parida, “Liquid phase bromination of phenol: II. Over heteropoly acid (HPA)-impregnated zirconium phosphate (ZrP)”Mol. Catal.A: Chem.305,P32(2006).
【54】D.P. Das, K.M. Parida, “Liquid phase bromination of phenol: III. Over heteropolyacid (HPA)-impregnated titanium phosphate (TiP)”Mol. Catal. A: Chem.253,P70(2006)
【55】A.P. Singh, S.P. Mirajkar, S. Sharma, “Liquid phase bromination of aromatics over zeolite H-beta catalyst”Mol. Catalysis A:Chem.150,P241(1999).
【56】吳明賢“Co(salen)錯合物和含鈷金屬孔洞異相觸媒的合成、鑑定及催化研究” 國立中央大學化學研究所碩士論文,P1(2008)。
【57】張金海“非均勻反應觸媒:特性與實效應用” 台南復文書局,P61(1994)。
【58】K. Tanabe, W.F. HoElderich, “Industrial application of solid acid base catalysts”Applied Catalysis A: General 181,P399 (1999).
【59】孫銘崑“聚麩胺酸水膠之交聯與應用”國立雲林科技大學化學工程系碩士論文,P4(2005)。
【60】M.A. Harmer, Q Sun“Solid acid catalysis using ion-exchange resins”Applied Catalysis A: General 221,P45(2001).
【61】Y.J. Li, M.S. Whittingham, “Hydrothermal synthesis of new metastable phases:preparation and intercalation of a new layered titanium phosphate”,Solid State Ionics,63,P391(1993).
【62】李英正,白御凌“層狀磷酸鈦做為反應觸媒的研究”聖約翰學報第二十五期,P213(2008).
【63】S. Mallick, K.M. Parida, “Studies on heteropoly acid supported zirconia II. Liquid phase bromination of phenol and various organic substrates”Catalysis Communications.8,P889 (2007).
【64】J. Muzart, “Chromium-catalyzed oxidations in organic synthesis”Chem. Rev.92,P113(1992).

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